TW422942B - Negative-type resist composition and process for forming resist patterns - Google Patents

Abstract

A negative-type resist composition which is developable in a basic aqueous solution, which comprises a film-formable, basic aqueous solution-soluble polymer with an alkali-soluble group, a compound with an allyl alcohol structure and a photoacid generator which when decomposed by absorption of image-forming radiation causes the compound with an allyl alcohol structure to become a protecting group for the alkali-soluble group, as well as a resist pattern-forming process which employs it. A basic aqueous solution can be used as the developing solution, and it is possible to form intricate patterns with a practical sensitivity and no swelling.

Description

422942 Imprint A7 _____B7_____ of the Consumer Goods Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (1) Background of the Invention The present invention relates to a negative photoresist composition that can be developed using a test aqueous solution, and to a pattern formation method. In recent years, LSI and VLSI circuits have been developed with the increasing integration of semiconductor volume circuits, and the minimum line width of wiring solutions has reached the sub-micron size. This requires the development of microfabrication technology, and in the field of etching, this demand has been met, whereby the ultraviolet wavelength from the exposure light source has been biased to a shorter wavelength in the deep ultraviolet region, but many studies have also proposed the use of far ultraviolet rays. Exposure method of light source with wavelength in the area. At the same time, the development of photoresistive materials with shorter wavelengths, lower absorbance and satisfactory sensitivity and high resistance to dry corrosion has been accelerated. Description of conventional techniques In recent years, more people have studied photolithography for the use of thorium fluoride excimer lasers (wavelength: 248 nm, hereinafter abbreviated as KrF) as a new exposure light source for semiconductor manufacturing. And these are about to be put into practical use. Photoresistants with high sensitivity and high recognizability that can match shorter wavelength light sources include photoresist compositions based on the concept of "chemical amplification", which is composed of H. Ito. Et al. Of IBM, US (JMJ Frenchet et al., Proc. Microcircuit Eng., 260 (1982), H. Ito et al., Digest of Technical Papers of 1982 Symposium on VLSI Technology, 86 (1983), H. Ito et al "" Polymer in Electronics " , ACS Symposium Series 242, T. Davidson, ed., ACS, 11 (1984), USP 4,491,628 (1985)) published the basic concept based on the use of photoresistance thin paper standards applicable _ National Standard (CNS) A4 specifications < 2 〖〇X 297mm） 4 ---- 1 --- ^ ------ install -------- order ---------- line (please read first Please fill in this page on the back of ii.) Printed on 422942 at .B7 by the Intellectual Property Bureau of the Ministry of Economic Affairs. V. Description of the invention (2) Table of the catalytic reaction in the membrane to improve the sensitivity and recognition. Quantum yield. Post-exposure bake (PEB) at the photoresist's illuminated area deprotects the t-BOC protecting group to produce isobutene and carbon dioxide, which is produced by receiving light An example of a chemically amplified positive photoresist obtained by adding PAG (photoacid generator) of acid to isobutoxycarbonylation (T-BOC) polyvinyl phenol (PVP) which has been widely studied and utilized. Deprotection reaction station The generated protonic acid is used as a catalyst to promote the deprotection chain reaction, so that the polarity of the illuminated area is changed considerably. Therefore, the photoresist pattern can be formed by selection and appropriate developer. In recent years, it is used Etching of shorter wavelength (wavelength: 193 nm) ArF (argon fluoride) excimer laser to produce high single-layer integration devices, such as billion-bit-level DRAM, has also accelerated research. Traditional phenolic resins are here The absorbance at the wavelength is longer, so the matrix resin must be changed. Therefore, it is urgent to develop a photoresist suitable for these shorter wavelengths. "Although there are many studies on the traditional positive chemically amplified photoresist suitable for ArF wavelength ( For example, K. Nozaki et al., Chem_ Mater., 6, 1492 (1994), K. Nakano et al., Proc. SPIE, 2195, 194 (1994), RD Allen et al., Proc. SPIE, 2438, 474 (1994), Japanese Patent Publication No. 9-9063 No. 7 and K. Nozaki et al., Jpn. J. Appl. Phys., 35,, L528 (1996), K. Nozaki et al., J. Photopolym. Sci. Technol., 10 (4), 545-550 (1997)), but there are very few single-layer negative chemically amplified photoresists, and even the photoresist composition contains a crosslinking agent to obtain a crosslinked negative pattern photoresist (such as A. Katsuyama et al. This paper size applies to China National Standard (CNS) A4 (210 X 297 Gongchu) --- ^ ---------------------.- ----- (Please read the precautions on the back before filling this page) A7 B7 422942 V. Description of the invention (3)

Abstracted Pares of Third International Symposium on 193 nm Lithography, 51 (1997), Maeda et al., Extended

Abstracts, the 58th Symposium on Applied Physics, No. 2647 (3a-SC-17) (1997)). These negative photoresists use the advantages of cross-linking reaction in the illuminated area to increase the molecular weight, so there is a difference in the solubility of the developing solution to the unlit area to obtain a negative pattern. It is inevitable that the pattern becomes large, which restricts the production of accurate micropatterns. Enhanced recognition technology has been widely studied in recent years. It uses a phase transfer cover instead of a double cover, and it is a promising technology to obtain a resolution lower than the wavelength of light. A negative photoresist is considered to be suitable for use with such a cover, and from this point of view, an ArF negative photoresist is also highly needed. These masks are considered to be applicable to situations where ArF light sources are required to obtain a resolution of 0.13 microns or less, and therefore efforts have been accelerated to develop solutions that can dissolve these micropatterns without becoming larger. Description of Examples The compound containing an allylase structure may include a structure of the following formula (I) or (II):

X

0H, where X represents a hydrogen atom or a linear, branched or cyclic alkyl group having another acryl alcohol structure, and η represents an integer of 2-7; this paper size applies Chinese National Standard (CNS) A4 specifications (210 X four 7mm) I'11'1 — 1 ·! — II 1 Order I-fjl! J (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

A7 Β7

Produced by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, Y produced, · 0Η (ΙΙ) where X is as described above, and γ represents a straight chain, branched chain or cyclic entertainment with at least two carbon atoms-itself has another woman Alcohol structure, and may also have another substituent. Refers to the "base-soluble polymer" of the matrix resin used in the photoresist composition of the present invention, which has a wide range of uses and includes different types of polymers, from homopolymers composed of a single monomer unit to including these monomer units and Copolymers of other desired monomer units (including terpolymers, etc.) The polymer used here is preferably a test polymer, where at least one of the structural monomer units is _ (methyl) propionate as Monobasic units of the matrix | that is, monomer units based on acrylic acid or methacrylic acid ester as bases, vinylphenol monomer units, and N-substituted maleimide Monomer units, monomer units based on stupid ethylene or monomer units with polycyclic aliphatic hydrocarbon substituents, more preferably polycyclic aliphatic hydrocarbons with adamantyl, probornyl, etc. as Monomer unit of typical structure. The photoresist composition of the present invention is preferably a composition having appropriate absorption characteristics at an exposure wavelength (1 nm) of 1.75 or lower, as a composition having appropriate characteristics. When an alkali-soluble polymer When in the form of a copolymer, Alkali-soluble; other monomer units used in combination with the monomer units of the group may have any structure 'as long as the polymer can maintain an appropriate alkali solubility in the developing solution. Even when the alkali-soluble polymer is in the form of a trimer There is no restriction 'As long as the polymer maintains its alkali solubility, these combinations are also preferred. In this case, ----- 1 ---- ^-I --- pack * II (please read first Please fill in this page again on the legal matters on the back) --line · -ϋ un. This paper size applies the Chinese National Standard (CNS) A4 Regulation (2J0 x 297 mm) 7 Printed by the Industrial Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 422942 V. Description of the invention (5) The first monomer unit having a test-soluble group can be used in combination with a second monomer having a weakly alkali-soluble group, and these combinations are also preferable. Photoresist composition of the present invention The substance is preferably present in the form of a solution dissolved in a solvent selected from the group consisting of ethyl acetate lactate'methylpentyl network acetate and mixtures thereof. The photoresist composition may contain, if necessary, selected from the group consisting of butyl acetate, γ- Butyrolactam 'propylene glycol methyl ether and its auxiliary solvents. In the method for forming a photoresist composition of the present invention, the photoresist composition that has been formed on the target substrate is preferably heat-treated before and after the selective illumination step. That is, according to the present invention, the photoresist film is The post-baking treatment is performed before the light irradiation, and also as the aforementioned PEB, the post-baking treatment is performed after the light irradiation and before the development (the post-exposure baking heat treatment can be advantageously completed by a conventional method. The alkali-soluble polymer of the present invention has an alkali The proportion of the monomer units of the soluble group need not be specified, as long as the resin itself exhibits sufficient alkali solubility, but in order to obtain an appropriate alkali dissolution rate (in the 2_38% ΤΜΑΗ developing solution that is considered to be practically applicable to negative photoresist) (Dissolution rate of 100 angstroms / second · 1000 angstroms / second), for example, in a polymer including two or more monomer components, monomer units having an alkali-soluble group are recommended The content is preferably 10 to 90 mole%, more preferably 30 to 70 mole%. If the content of these monomer units is less than 10 mole%, the alkali solubility is insufficient to achieve a satisfactory sample preparation. However, if it exceeds 90 mole%, the alkali solubility will be too high, resulting in an alkaline aqueous solution. The dissolution rate is too high to achieve sample preparation by changing polarity. The content of these monomer units is more preferably 30-50 mol%. The content of compounds with allylase structure will depend on the alkali solubility in the polymer mist

The size of this paper is in accordance with the National Standard (CNS) A4 (210 X 297). Installed -------- Ordered ------------ Thread (please 'M read the back first Please note this page and fill in this page again) A7 422042 ------ B7___ V. Description of the invention (6) The number of groups, that is, the rate of alkali dissolution, but for polymers with the above-mentioned proper alkali dissolution rate The recommended amount is% by weight (based on the weight of the polymer). A better amount is 10.4% by weight. The content of β photoacid generator (PAG) will depend on the acid generated when exposed to light sources. The concentration depends on the concentration, but it is generally recommended to be 0-15% by weight (based on the weight of the polymer), and more preferably 1-15% by weight. The weight average molecular weight of the polymer used in the present invention is recommended to be 2,000 (M, 0.00, The range of 〇〇〇, more preferably 3000-50,000. The solvent added to the photoresist composition does not need to depend on the solubility of the solute, but for low solubility solutes, it is generally preferred to add Calculated as the main solvent) 'more preferably 10-20% β The alkaline aqueous solution used as the developing solution may belong to Groups j and II of the periodic table Metal hydroxides, such as aqueous potassium hydroxide solution, or organic aqueous solutions without metal ions, such as argon-oxidized tetrahydroxanthol; optimally tetramethylammonium hydroxide (TMAΗ), and various additives, For example, a surfactant can also be added to enhance the developing effect. It is clear from the following detailed description that the photoresist composition and photoresist formation method of the present invention can be completed by several different preferred embodiments. The invention relates to a chemically amplified photoresist composition, which can use a basic aqueous solution to form a negative photoresist pattern on a target substrate. The photoresist composition system includes (a) a film-forming polymer containing alkali-soluble groups, which It can dissolve itself in an alkaline aqueous solution of ((b) a compound having an allyl alcohol structure, and (c) PAG (photoacid generator) ', which decomposes upon exposure to light and can produce a paper standard that is applicable to Chinese national standards ( CNS) A4 specification (210 X 297 public love) ^: Packing --- 靖 Jing first read the note on the back before filling out this page) " .line. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives * 1 Take A7 422342 B7______ V. Description of the invention (7> The acid having a solubility-restricted group protected by a dilute propanol compound, wherein the compound having a propanol structure has a structure represented by formula (I) or (II). The present invention The mechanism behind the chemical amplification of the photoresist composition is as follows. The explanation is based on the use of a carboxylic acid as the alkali-soluble part of the alkali-soluble polymer, and a compound of the formula (〖) as a compound having an allyl alcohol structure. When the PAG in the photoresist composition irradiates an image to form radiation after the photoresist film has been formed, it absorbs the radiation and generates an acid. When the illuminated photoresist film is then heated, the generated acid plays a catalytic role to promote the subsequent esterification reaction in the illuminated area of the film to reduce the polymer's solubility. ^ Γ! Ί · install i I (Please read the notes on the back before filling this page) ο poLymer main chain

+ Η 0Η polymer main chain 7 / ο

X Η ". Printed in the photoresist composition of the present invention by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Line Economy, alkali-soluble groups are included in the matrix resin, and are also included in formula (I) or (π) Among the compounds shown as having an allyl alcohol structure, the soluble group can be protected when heated in the presence of an acid catalyst. "Because this is a type of amplification of a proton acid due to a protection reaction, it can achieve high sensitivity. When the alkali-solubility is lost after the reactive groups have been protected (the ester conversion described above), the illuminated area of the photoresist film becomes insoluble with alkali, so a negative pattern is formed after development with an alkaline aqueous solution. According to the present invention, it is possible to obtain a case that does not change in size, because the circle case is based on the Chinese paper standard (CNS) A4 (210 X 297 mm) 10 A7

422942 V. Description of the invention (8) It is formed by changing the polarity generated in the photoresist. As the alkali-soluble polymer in the photoresist composition of the present invention, especially in the form of a trimer, it has a strong alkali-soluble group in the first monomer unit, of which a carboxylic acid is a typical example, but the second monomer unit Contains weakly alkali-soluble groups with a lactam ring structure, acid anhydride, and imine ring structure. In this case, the content of the strong alkali-soluble groups and the weak alkali-soluble groups can be controlled to easily adjust the alkali-soluble rate of the matrix resin. To the desired value. The third monomer unit may be a monomer unit having a functional group that is resistant to starting, and this is very necessary for a photoresist. The structure of the alkali-soluble polymer serving as the matrix resin in the photoresist composition of the present invention is not particularly limited as long as it satisfies the above-mentioned conditions, especially the conditions with an appropriate alkali-dissolving speed ', but if the anti-drying property comparable to that of novolac resin is reached When corrosivity is a consideration, it is recommended to use monomer units with propylene glycol as the base or monomer units with fluorenyl acrylate as the base, a vinyl phenol polymer, and maleic acid substituted with N. Polymers of eneimine as matrix, polymers of styrene as matrix, etc., polymers with polycyclic aliphatic hydrocarbon compounds in the ester group. In particular, polymers based on acrylic acid and based on methacrylic acid are important because they have low absorbance when using deep ultraviolet rays, particularly ultraviolet rays having a wavelength of 250 nm, as the light source. In other words, when deep ultraviolet light is used as a light source, it is preferable to use a polymer having an aromatic ring structure that does not strongly absorb light in the deep ultraviolet region, or a chromophores having a high extinction coefficient, such as conjugated double bonds (chromophores). ) ° In particular, when using a light source with an extremely short wavelength range of the illumination wavelength, this paper is also applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm>.): -------- Order- --.------ line (Jing first read the precautions on the back and then fill out this page) 11 mm Λ printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs; At the time of laser, the dry-resistance and transparency at this wavelength (193 nm) become necessary properties. Therefore, it is recommended to use a polycyclic aliphatic hydrocarbon structure containing adamantyl'orbornyl group as the typical one. Acrylate-based, highly dry-resistant polymers, especially polymers based on acrylates and methacrylates β Polymers based on acrylates or methacrylates, or other The molecular weight range of the alkali-soluble polymer can be very wide, but it is preferably 2,000 to 10,000, more preferably 3,000 to 50,000. It can be advantageously used for The alkali-soluble polymer for carrying out the present invention includes, but is not limited to, the following exemplified polymers. In the following formula, 1, m and η represent the number of monomer units (repeating units) required to obtain the above weight average molecular weight, unless It is also stated explicitly that the heart system represents any desired substituent such as a hydrogen atom, a halogen atom (chlorine, bromine, etc.), a low-carbon alkyl group (methyl'ethyl, etc.), a cyano group or the like, which Can be all the same or different ----: ----: ------ install -------- order_ (please read the precautions on the back before filling this page) (1) Acrylic acid Ester-based and methacrylate-based polymer printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Hc R — c —

R

R Ηο Η ο

—C 2 Η Rο ο 7 /

IC Rο In this structural formula, R4 represents a weakly alkali-soluble group, and its representative example is an internal amine ring, but the unit containing 鳢 is not a necessary unit, as long as 12 paper standards are applicable to the Chinese standard ⑽x 297- 巧422942 A7 V. Description of the invention (〖〇) The alkali dissolution rate is a value suitable as a negative photoresist matrix resin. h may be a desired neutral functional group, and it may be appropriately selected according to the transparency and corrosion resistance at the wavelength of the light. In order to improve the adhesion of the photoresist to the substrate, it may also contain a neutral group. , Such as ketone or hydroxyl. In addition, the following compounds having a structure containing an ester group and having a carboxylic acid group as an alkali-soluble group are of course acceptable.

R Η c

C

Η C

2 R— C

R

Z Η C

C

C

C

G ο ο. Ο R ο ο R ο

X R \ C OOH In this structural formula, R4 & R5 has the same definition as above. Rx can have any desired structure, but the preferred choice is similar to R5. (2) The following polymers include units based on styrene as alkali-soluble units. -JI! 7 I ill ---- Order ---.----- line (Please read the precautions on the back before filling out this page} Printed by the Intelligent Property Bureau of the Ministry of Economic Affairs

Rt ί — ^ CH * —C >

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 422942 A7 _B7_ V. Description of Invention (11) In this structural formula, Ry represents any desired substituent. The heart is preferably selected as described. (3) The following polymers containing units based on trans-butenedioic acid as base-soluble groups: COOH i —eCH — —! C 0 0 Rs (4) The following units containing vinylbenzoic acid as base Polymer as an alkali-soluble group. R. I C Η 2 -C) ~ 5

In this structural formula, the heart system is the same as described above. (5) The following polymers containing units having orbornene carboxylic acid as a base as alkali-soluble groups.

COOH This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 14. Τ ------ installation -------- order ---: ------ line (Please read the precautions on the back before filling this page) Cancer M following A7 B7 V. Description of the invention (i2) (6) The following polymers containing units with mesuccinic acid as the matrix as alkali-soluble groups β 〇II CHjC — 〇RsIecHi — CHiCOOHI ^ CH 2 — C-)-5—

c // \ 0 OH C \ 0 OR: ⑺ The following polymers contain cis-succinic acid as the matrix-soluble unit as the test group. — ^ CH *-CH ^ — / HOOC Λ // \ 〇 OR, (8) The following polymers containing a vinylphenol-based unit as an alkali-soluble group. ----: -------- ^ -------- ^ ---.------ line I — {Please read the precautions on the back before filling this page] Ministry of Economy Wisdom Printed by the Property Agency Staff Consumer Cooperative

Ry

OH As mentioned above, these polymers can also be combined with other suitable units to form any desired copolymer (containing 3 or more components). A more specific example of an alkali-soluble polymer useful in the present invention is A polymer represented by the following formulae (III) to (XV). This paper size applies to the national standard (CNS) A4 specification (210x297 mm) 15 42 ^ 42 A7 _B7 V. Description of the invention (13)

Η Η \ c J— C'C 1 Λν 2 Η C ο Η ο ch3 t -H 2 —C H) ~ r 0 // c

OH Η c

3 \ τ Η Η CICIC

Η C

Η Η C ——C — C ο

C

Η cue 1I Η CIC

ο y R R ο (III)

Η C ο ο ο 7 /

Η Η clcIC R ο V 1

CH 〇

C H3! 2-C H) S ~~ I C々 \ 0 OR (V)

(VI) ---- ^ ---- J ------------ Order ----- I! (Please read the notes on the back before filling this page) Intellectual Property of the Ministry of Economic Affairs CHiI -fC H2 —C —m 6C H i C ~ s ~

C & \ 0 ORi This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) 16 (VII) 422942 A7 B7 V. Description of the invention (14) C Hj I —ectu —ch) ic // 0

C Hj! —Ί-CH—C H > —5 ~~ fC Hi —CH) —s1 I t GC / c, // \ / W \ np 〇H 0 NO 〇0Rs H (VIII) CH3t-^ c Hz --CH) m-^ c Ηϊ --C HW- (IX) R y

O // c ORj (x)

OH OR

-^ C H a -C Η >-«~~ ¢ -0 H 2 —C

OR (XI) ^ 1 ^ 1 ^ 1 ^ 1 ^^ 1 * ^ 1] K n E t 1-^ 1 nn I nnn fft nn I < Please read the notes on the back before filling this page): CHz — CH ^

(XU) Consumption Cooperation by Employees of Intellectual Property Bureau, Ministry of Economic Affairs

(XIII) This paper size is in accordance with Chinese National Standard (CNS) A4 (210x297 mm) 17 422942 A7 B7 V. Description of the invention (15 c h3 c h3 —fC H2 —CH) -T ~ ec H2 — (CH? — C Hh

R y

COOH

OR: C Hi (XIV) C H2 —C -fC H; —C Η > -ττ R y ^ —〇 〇 0 0 R i

OH (xv) These are only examples and the structure is not limited thereto. Similarly, 1 ^ and 115 in these structural formulas are as defined above and R is to select any desired functional group similar to R5, but compounds whose structure does not dissociate from the acid are preferred for the constitution of photoresist. The following compounds have a structure which becomes a typical functional group which can be advantageously used in these structural formulas. (1) Compounds based on adamantyl ---------- install -------- order ---.------ line {Please read the intention on the back first Please fill in this page for further information) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

Γ7 ^ ΌΗ

OH This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 18 422942 A7 B7 V. Description of the invention (16

OH Μ

Μ

OH

〇

Ο 0 R Ο (2) Orthobornane compounds

OH

HO

HO

OH

------- I ------- install ------ order ij ------- line (please read the business matters on the back before filling this page) employee of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Consumer Cooperatives

〇 ^ br ° 〇

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 19

422942 A; --BZ_ V. Description of the invention (17) (3) Compounds based on dicyclopentadiene (dagger represents hydroxy fluorene or alkoxycarbonyl)

The above formulae (I) and (II) refer to allyl alcohol-based compounds to be added to the matrix resin, but more specific examples of the compounds which can be used favorably include the following compounds. (1) Cyclic allyl alcohol ο ------- ^ ---- 1.P Pack! ---- Order -----!! (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 0 S OiC f3 .0 S 0 a CF 3 0 S OiC F 2) Linear allyl alcohol

20 This paper size applies to China National Standard (CNS) A4 specifications (21 × 297 mm) A7 B7 422942 V. Description of the invention (α The alkali-soluble polymer proposed by the present invention can be generally used for polymers by using Prepared by a chemical polymerization method. For example, an advantageous method of preparation includes heating a specified monomer component in the presence of AIBN (2, 2'-azobisisobutyronitrile) as a free radical initiator. Except for methyl groups Alkali-soluble polymers other than acrylate-based polymers can also be advantageously produced by established methods. Methacrylate polymers are known to have high transparency in the deep ultraviolet region, and also in the structure and Among the added dilute propanol compounds, 'with a high extinction coefficient in the wavelength range BO-250 nanometers by proper selection of a structure that does not have color development problems', its combination with an appropriate amount of pag (photoacid generator) will be used in use A highly sensitive photoresist that responds favorably to light in deep ultraviolet light. The above-mentioned alkali-soluble polymer has a base that can be protected by an acid catalyst reaction in the presence of an allyl alcohol compound. It can provide high sensitivity in the protective reaction of protonic acid. Because the soluble group is protected after the protective reaction, the exposed area of the photoresist film becomes insoluble in alkaline solution ' The negative pattern is developed by dissolving the non-light-receiving region. Here, the pattern obtained does not become large because the polarity change in the matrix resin is used. * In the chemically amplified photoresist of the present invention, the above is polymerized with an acid sensitive polymer The PAG used in combination can be pAG generally used in photoresist chemistry. In a word, it is a substance that generates protonic acid when it is irradiated by ultraviolet, far ultraviolet, vacuum ultraviolet, x-ray and other radiation. It can be used in The PAG of the present invention includes, but is not limited to, the following substances. ----_--------! Equipment -------- Order.! -------- Line (read first (Notes on the back, please fill out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 21 0

mm a7 _B7_ V. Description of the invention (19) (1) 锵 Salts: (R ._) 2 — I + X-

(r ") 3-sV In this formula, R ”represents a substituted or unsubstituted aromatic ring or an aliphatic group, and X represents BF4, PF6, AsF6, SbF6, CF3S03, C104 and the like (2) sulfonic acid ester:

CH; 0 S 〇2C F3 S 〇2C F j ----; -------- install -------- order --------- line {Please read the note on the back first Please fill in this page again) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 0 S O2C f3 (3) Toothed compounds:

X3C N C Xr γ N _ N

Vc x3

X

X

X = C 1. B 22 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 422942

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (20) These PAG (photoacid generator) compounds can be used in various amounts in the photoresist composition of the present invention. The amount of PAG used is suggested to be 0.uo% by weight (based on the weight of the polymer) ', more preferably 1-15% by weight. However, the structure of the polymer and the amount of PAG are preferably such that the absorbance at the wavelength of the light is not more than 1.75. The photogroup composition of the present invention can generally be advantageously used in the form of a photoresist solution ', which is preferably prepared by melting the above-mentioned alkali-soluble polymer, allyl alcohol compound and PAG in a suitable organic solvent. Useful organic solvents suggested for the preparation of photoresist solutions include ethyl lactate, methylpentyl ketone, methyl-3-methoxypropionate 'ethyl-3_ethoxypropionate, and propylene glycol methyl ester. Methyl acetate is' but not limited to these compounds. These solvents can be used alone, but two or more solvents can be mixed as necessary. The amount of the solvent is not particularly limited, but it is preferably sufficient to obtain a viscosity suitable for coating the desired photoresist film thickness by spin coating or the like. The amount β is as needed. In the photoresist solvent of the present invention, auxiliary auxiliary agents other than the above solvents (main solvents) may also be used. The auxiliary solvent can depend on the solubility of the solute and the uniformity of the coating of the solution. It is not necessary to use it, but it is usually better to add 1-30 based on the main solvent when the solubility of the solvent is low and the uniformity of the coating is not satisfactory. % By weight, more preferably 20% by weight of the auxiliary dropping agent. Examples of useful auxiliary agents include, but are not limited to, butyl acetate, r-butyrolactam, propylene glycol methyl ether, and the like. The present invention also provides a method for forming a photoresist case, particularly a negative type case, on a target substrate using the above-mentioned photoresist composition. The negative type photoresist pattern of the present invention can be generally formed in the following manner. This paper size applies to China National Standard (CNS) A4 specifications (21CU 297 male cage) • H ϋ n I nn ^ UJ n I n ί t— t (Please read the note on the back first? #Item and then fill out this page) 23 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 422942 V. Description of the Invention (2!) First, the photoresist composition of the present invention is coated on the target substrate to form a photoresist film. The target substrate may be a substrate generally used in a semiconductor device or other devices, such as a silicon substrate, a glass substrate, a non-magnetic ceramic substrate, and the like. These substrates may have other layers on the upper side thereof, such as a oxidized oxide film layer, a wiring metal layer, an interlayer insulating film layer, a magnetic film, and the like, and various wirings or circuits may be incorporated therein as necessary. These substrates can also be subjected to a hydrophobic treatment using a common method to increase their adhesion to the photoresist film. It can be proposed that the coating of 1,1,1,3,3,3 -hexamethyldicarboxylate ammonium sulphate (HMDS) can be applied on the target substrate in the form of a photoresist solution as described above. Way to complete. The photoresist solution can be applied by a spin coating method, a roll coating method, a dip coating method, or other general techniques, but a spin coating method is particularly useful. The thickness of the photoresist film is recommended to be about 0.1-200 μm, but when KrF ′ ArF or other excimer laser is irradiated, it is recommended to be 0.1-1.5 μm. The thickness range of the photoresist film formed can vary depending on many factors, including applications. The photoresist film that has been coated on the substrate is preferably pre-baked at a temperature of about 60-180 ° C for 30-120 seconds before it selectively irradiates the image to form radiation. The pre-baking step can be accomplished by using a general heating device used in the resist process. Examples of suitable heating devices include hot plates, infrared heating ovens, and microwave heating ovens.

I Pre-baked photoresist film and then selectively irradiate the image with a general exposure device to form radiation. • Suitable exposure devices include commercially available ultraviolet (deep ultraviolet) exposure devices, X-ray exposure devices, and electron beam exposure. The device and the paper size are applicable to the National Standard (CNS) A4 specification (2) 0 * 297 mm. — — — — — — — —-. IIII — II ^ imln (please read the back first) Note i, please fill in this page again) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 421042 at -------- B7_____ V. Description of the invention (22) Other devices. The exposure conditions can be appropriately selected, and according to the present invention, excimer lasers (248 nm KrF laser or 193 nm wavelength laser) can be advantageously used as exposure light sources, "radiation," means from these light sources Any of these wheel rays. The PEB is passed through the photoresist film of the light, and the protective reaction of the soluble group is generated by the acid catalyst. The post-exposure baking step can be completed in the same way as the previous test step, for example, to perform sufficient For example, the baking temperature can be about 60-18 ° C, and the baking time is about 30-120 seconds, but this is preferably based on the size and shape of the case. After PEB, the alkali as a developing solution The photoresist film is developed in a neutral solution. For development, a general development device such as a rotary developer 'impregnated developer', a spray developer, or the like can be used. The alkaline aqueous solution as the developing solution may belong to the periodic table. Argon oxides of metals of Groups I and II, such as aqueous solutions of potassium hydroxide, or aqueous solutions of organic bases without metal ions, such as tetraalkylammonium argon oxide; most preferably hydrogen Tetramethylammonium (TMAΗ), and various different additives, such as surfactants, can also be added to enhance the development effect. 6 Development causes the solution in the unlit area of the photoresist film to fall off, so that only the negative type in the illuminated area The photoresist pattern remains on the substrate-the following examples are used to explain the acid-sensitive polymer of the present invention in more detail; the related synthesis of the photoresist composition and the formation of the photoresist package. These are just implementation The examples are not intended to limit the scope of the present invention. Example 1 The matrix resin is poured into a methacrylic ring at a ratio of 5: 2: 3. The paper size is applicable to the national standard (CNS) A4 specification (210 X 297). (Li) I 丨 丨 丨 I! ------ install -------- order ------- line (please read the precautions on the back before filling this page) 25 Intellectual Property Bureau, Ministry of Economic Affairs Printed by the Consumer Cooperative 422942 a7 __________B7____ 5. Description of the invention (23) Hexyl ester, butyromethamine-2-methyl methacrylate and methacrylic acid are poured and synthesized. The obtained resin is dissolved in PGMEA (propylene glycol methyl ether acetic acid) Xue) to obtain 15% by weight solution 40% by weight of cis-verbenol and 10% of butyrolactam were added to the solution. 2% by weight of trifluoromethanesulfonic acid triphenylsulfanil was added and completely dissolved in the solution. 2 The photoresist solution obtained from the thin film iron reducer is then spin-coated on the broken substrate that has been treated with HMDS, and it is pre-baked at no C for 60 seconds to form a 0-7 micron thick Photoresist film. After placing it in a KrF excimer laser stepper (NA = 0.45), baking at 120 ° C for 60 seconds' and then oxidizing tetramethylammonium (TMA) with 2.38% argon The developing solution is developed and rinsed with deionized water. A dose of 14.0 millijoules per square centimeter yielded a discrimination of 0.25 4 mL / S. Example 2 The photoresist solution of Example 1 was used in the same manner to form a 0.5 micron-thick photoresist film on a silicon substrate that had been treated with HMDS. After the substrate was placed in an ArF excimer laser exposure device (NA = 0.55), the substrate was developed at 120 ° (: baking for 60 seconds, and then developed with 2.38% tetramethylammonium hydroxide (but 1 ^ 11)). The solution was developed and rinsed with deionized water. 0.20 was obtained at a dose of 4.2 millijoules / cm 2; the discrimination of tzmL / S was obtained. Example 3 The obtained resin was dissolved in 15% PGMEA, and then 40% by weight of the resin was used. 3,5,5-trimethyl-2-cyclohexene and 10 weight of butyrolactam were added to the solution. Similarly, a 2% by weight portion of diphenyliodine trifluoromethanesulfonate was added to the resin as a light. Resistor. It is spin-coated on the paper that has passed the national standard of this paper. (CNS) A4 specification (210 * 297 mm) 26 II 1 i! J ^ -------- I .-- ---- $ 1 — (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs __b7_ V. Description of Invention (24) HMDS-treated silicon substrate, and then 110 ° c Pre-baked for 60 seconds to form a 0.5-micron-thick photoresist film. "After placing it in an ArF excimer laser exposure device, baking at 130 ° C for 60 seconds, and then oxidizing tetramethyl at 2.38% argon Developed with ammonium (TMAH); developed in the valley solution and rinsed with deionized water. A dose of 3.4 millijoules / cm² was obtained with a resolution of 0.18 / zmL / S. Example 4 The alkali-soluble polymer of Example 1 was dissolved. At 15% PGMEA, 3-methyl-2-cyclohex-1-ol and 10% butyrolactam as auxiliary solvents were added to the solution at 50% by weight of the resin. Similarly, 2% by weight Diphenyliodonium trifluoromethanesulfonate is added to the resin as a photoresist. It is spin-coated on a silicon substrate that has been treated with HMDS and then pre-baked for 60 seconds with no X: to form a 0.5 micron thick photoresist The film was placed in an ArF excimer laser exposure device, baked at 120 ° C for 60 seconds, and then developed in a 2.38% argon oxide tetramethylammonium (TMAH) developing solution and rinsed with deionized water. The discrimination obtained at a dose of 3,4 millijoules per square centimeter. Example 5 The alkali-soluble polymer of Example 1 was dissolved in 15% PGMEA, and geraniol, which was 40% by weight of the resin, was used as an auxiliary solvent. 10% by weight of T-butyrolactam was added to the solution. Similarly, 2% by weight of trifluoro (methanesulfonate) was added. Resin was added as a photoresist to the styrenic iron. It was spin-coated on a silicon substrate that had been treated with HMDS, and then pre-baked in a 110 ° process for <50 seconds to form a 0.5 micron thick photoresist film. After placing it in an ArF excimer laser exposure device, baking at 130 ° C for 60 seconds, and then oxidizing tetramethyl methacrylate at 2.38% argon. This paper is compliant with China National Standard (CNS) A4 (210 X 297 mm) 7 : ------ install -------- order --------- line (please read the unintentional matter on the back before filling this page) 27 422342 A7 _______B7__ V. Description of the invention ( 25) Develop in a TMAH developing solution and rinse with deionized water. 4.0 millijoules per square centimeter to obtain 0.20 / zmL / S recognizability "&lt; Please read the precautions on the back before filling this page) Example 6 Matrix resin is poured into a ratio of 5: 1: 4 It is synthesized by pouring adamantyl methacrylate, methylene succinic anhydride and methacrylic acid. This was dissolved in PGMEA (glycerol methyl bond acetate) to obtain a 15% by weight solution. Also added to the solution were cis-verbenol and 40% by weight of T-butyrolactam, which constituted 40% by weight of the resin. A 2% by weight portion of trifluoromethane ditrimethanesulfonate was added and completely dissolved in the solution. The resulting photoresist solution was filtered through a 0.02 micron Teflon membrane filter, and then spin-coated on a silicon substrate that had been treated with HMDS. It was pre-baked with uOec for 60 seconds to form a 0.5 micron thick Photoresistive film. After it was put in an ArF excimer laser exposure device, it was baked at 130 ° C for 60 seconds' and then developed with a 2.38% argon oxidized tetramethylammonium (TMAH) developing solution and rinsed with deionized water. A dose of 4.4 millijoules / cm² was obtained with a discrimination of 0.20 / zmL / S. Example 7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The matrix resin was synthesized by pouring vinylphenol and adamantyl methacrylate in a ratio of 8: 2. It was dissolved in PGMEA (propylene glycol methyl ether acetate) to obtain a 15% by weight solution, and also cis-verbenol, which is 35% by weight of the resin, and 10% by weight, which is an auxiliary solvent, 7-butane Amine was added to the solution. A 4% by weight portion of triphenylsulfanyl trifluoromethanesulfonate was added and completely dissolved in the solution. The resulting photoresist solution was filtered through a 0.2 micron Teflon membrane filter, and then spin-coated on a silicon substrate that had been treated with HMDS, and it was pre-baked at 110 ° C for 60 seconds to form 28 micron-thick paper. Standards apply to China National Standard (CNS) A4 specifications (210 X 297 meals) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 422342 A7 _. ____ B7 V. Description of the invention (26) Photoresist film. After putting it in a KrF excimer laser exposure device (Na = 0.45), it was baked at 130t for 60 seconds, and then oxidized tetramethylammonium (TMAH) with 2.38% argon. The developing solution was developed and rinsed with deionized water. . A dose of 10.0 millijoules per square centimeter obtained a discrimination of 0.25 # mL / S. Example 8 A matrix resin was synthesized by pouring vinyl phenol, cis-succinic acid needle and fluorenylpropionate cyclohexyl in a ratio of 7: 1: 2. This was dissolved in PGMEA (propylene glycol methyl ether acetate) to obtain a 15% by weight solution. Also added to the solution was cis-verbenol, which is 35 wt% of the resin, and 10 wt of butyrolactam as a co-solvent. A 2% by weight portion of diphenylmethane diphenylsulfanate was added and completely dissolved in the solution. The photoresist solution obtained by passing the 0.2 μm Teflon membrane filter through the solution was then spin-coated on the photoresist solution. On a silicon substrate treated with HMDS, it was pre-baked for 60 seconds in 1 10 to form a 0.7 micron-thick photoresist film. After putting it in a KrF excimer laser exposure device (NA = 0.45), it was baked at 130βC for 60 seconds, and then developed with a 2.38% argon oxidized tetraflammonium (TMAH) developing solution and rinsed with deionized water. A dose of 14.0 millijoules / cm 2 was obtained with a degree of discrimination of 0.25 / zmL / S &lt; Example 9 The matrix resin was obtained by pouring a vinyl benzate 'maleic acid diene in a ratio of 3: 2: 5. Imine and adamantyl methacrylate are synthesized by pouring.

I It was dissolved in PGMEA (propylene glycol methyl ether acetate) to obtain a ^ wt% solution. Also added to the solution were cis-verbenol and 40% by weight of the resin and 10% by weight of 7-butyrolactam as an auxiliary solvent. Will be 2 weights This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love) 29 --------- installation ---- I --- nails ------! · Wire (Please read the precautions on the back before filling this page) 422942 A7 B7_ V. Description of the invention (27)% part of trifluorosulfanylsulfonium triphenylsulfide is added and completely dissolved in the solution. The resulting photoresist solution was filtered through a 0.2 micron Teflon film filter, and then spin-coated on a silicon substrate that had been treated with HMDS, and it was pre-baked at 110 ° C for 60 seconds to form a 0.7 micron thick photoresist film. After putting it in a KrF excimer laser stepped irradiator (NA = 0.45), it was baked at 130 ° C for 60 seconds, and then developed with a 2,38% argon oxidized tetramethylammonium (TMAH) developing solution. Rinse with deionized water. A dose of 17.5 millijoules per square centimeter yielded a discrimination of 0.28 in mL / S. Example 10 Comparison of dry-etching resistance The photoresist of Examples 1, 4, 6, and 9 was used to form a photoresist film having a thickness of 1 micrometer on a silicon substrate. For a commercially available novolac photoresist, Nagase Positive Resist NFR-820 (product of Nagase Sangyo) and PMMA (polymethyl methacrylate), using a parallel plate RIE device at Pu = 200W, pressure = 0.02 Torr and CF4 Etching was performed for 5 minutes under the condition of gas = 100 sccm, and the film loss amount of the sample was compared. Photoresist etching speed (Angstroms / minute) Rate ratio NPR-820 530 1 PMMA 805 1.52 Example 1 678 1.28 Example 4 700 1.32 Example 6 562 1.06 Example 9 600 1.03 These results show that the photoresist of the present invention The corrosion resistance is close to that of novolac photoresist NPR-820, but it is also suitable for the photoresist of Example 6 of ArF exposure. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) lift ..-- -.------ install ------- 1 order · —.----- line &lt; please read the notes on the back before filling out this page) Manufacture 30 42 £ u42 A7 ___B7_ 5. Description of the invention (28) The agent exhibits approximately the same contact resistance. Example 9 which is suitable for KrF The photoresist exhibits comparable resistance to novolac. This experiment also confirmed that all photoresists were better than PMM A. By using the photoresist composition of the present invention, it is possible to form a complex negative photoresist pattern that has practical sensitivity and does not become large. In addition, when the alkali-soluble polymer used in the photoresist composition is a terpolymer containing a strong alkali-soluble group in the first monomer unit, however, the addition of allyl alcohol as a protective base-soluble group is difficult. The matrix compound system allows the acid catalyst reaction to be exerted 'to obtain a higher sensitivity than the conventional photoresist composition. Moreover,' because the photoresist composition of the present invention is based on a change in polarity rather than a traditional cross-linking method. Therefore, it can easily achieve high contrast and recognition. When the polycyclic aliphatic compound structure is contained in the third monomer unit, especially when it has an adamantyl structure, the RJE resistance in the deep ultraviolet region is high. In addition, the transparency is high, so it can provide a novel and highly sensitive negative photoresist that is applicable to even short-wavelength exposure light sources such as ArF excimer lasers. ----; ---; ------ install -------- order ---.------ line &lt; Please read the precautions on the back before filling this page》 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, Paper Size Applicable Countries -Γ1Γ:-

Claims (1)

Α8 BS C8 D8 Ιί2ϋϋ42, patent application scope 1. A negative photoresist composition that can be developed in an alkaline aqueous solution, which includes a polymer that can form a film, is soluble in an alkaline aqueous solution, and has an alkali-soluble group. A compound having an allyl alcohol structure and a photoacid generator. The photoacid generator is decomposed as soon as it is absorbed to form radiation, causing the compound having an allyl alcohol structure to become a protective group for the alkali-soluble group. 2. The photoresist composition according to item 1 of the patent application scope, wherein the alkali-soluble polymer includes at least one derived from a group selected from the group consisting of acrylic acid, methacrylic acid, succinic acid, ethyl benzoate or A unit of a compound of dicyclohept-5-ene-2-carboxylic acid, vinylphenol, styrene and its derivatives. 3. The photoresist composition according to item 1 of the patent application scope, wherein the alkali-soluble polymer includes one or more weak alkali-soluble groups selected from the group consisting of a linamine ring, a imidate ring, and an acid anhydride. 4. The photoresist composition according to item 1 of the patent application scope, wherein the alkali-soluble polymer includes an aliphatic hydrocarbon portion or a polycyclic aliphatic hydrocarbon portion. 5. The photoresist composition according to item 4 of the scope of the patent application, wherein the polycyclic wax group hydrocarbon structure contains a structure selected from the group consisting of adamantyl, probornyl and bicyclic [2.2.2] octyl. 6_ The photoresist composition according to item 5 of the application, wherein the polycyclic aliphatic hydrocarbon portion contains at least one hydroxyl group or ketone group, or both. 7. The photoresist composition according to item 1 of the scope of the patent application, wherein the compound having a dilute propanol structure includes a structure represented by the following formula (I) or (II): This paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) — — — — — — — — — '1111111 ---, ------ 11 (Please read the notes on the back before filling out this page) Intellectual Property Bureau Employee Consumer Cooperatives, Ministry of Economic Affairs Printing 32 422942 A8 B8 C8 D8 6. Scope of patent application CCH2) „(!) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs where X represents an argon atom or a straight-chain 'branched or cyclic alkyl group with another acryl alcohol structure, and η represents an integer 2-7; Υ &quot; ^-ΟΗ (ΙΙ) where X is as described above, and γ represents a straight-chain 'branched or cyclic alkyl group having at least two carbon atoms, which may itself have another propylene alcohol structure' and may also have Another substituent. 8. The photoresist composition according to item 1 of the scope of the patent application, wherein the compound having a glycinol structure includes an alicyclic structure or a polycyclic aliphatic structure. 9. According to item 1 of the scope of the patent application A photoresist composition, wherein the compound having an allyl alcohol structure includes, in addition to an allyl alcohol molecular portion, at least one hydroxyl group, a keto group, or an alkyloxycarbonyl group. 10. According to the light of the first patent application scope The resist composition has an absorbance of 1.75 or less at the wavelength of the light source for image formation. 11. The photoresist composition according to item 1 of the patent application scope, which comprises at least one member selected from the group consisting of ethyl lactate and methyl hydrazone. Methyl ketone, methyl-3-methyl Solvents for methyl propionate, ethyl-3-ethoxy propionate and propylene glycol methyl ether acetate. 12 'Photoresist composition according to item 11 of the scope of patent application, further comprising a member selected from the group consisting of acetic acid Butyl ester, butyroylamine and propylene glycol methyl This paper applies the Chinese National Standard (CNS) A4 Regulations (2) 0 X 297 mm. ----------, ------ pack. 1 — (Please read the precautions on the back before filling this page) Order. Line · 33 B8 C8 D8 422342 6. Solvent for patent application_ 13. A method for forming a photoresist pattern, which includes the following steps: apply The photoresist composition described in items 1 to 12 is coated on a target substrate, and the formed photoresist film is selectively irradiated with an image that can decompose the photoacid generator in the photoresist composition to form radiation. And use an alkaline aqueous solution to develop the illuminated photoresist film β !!! 11-* --- IIII Order. Ί — ί— (Please read the precautions on the back before filling this page) Staff of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Consumer Cooperatives 34 This paper is sized for China National Standard (CNS) A4 (2KM 29 7 mm)